Raman Spectroscopy
Raman spectroscopy is a well-known technique for analyzing molecules or materials. In conventional Raman spectroscopy, high intensity monochromatic radiation provided by a radiation source, such as a laser, is directed onto an analyte (or sample) that is to be analyzed. In Raman spectroscopy, the wavelength of the incident radiation typically is varied over a range of wavelengths within or near the visible region of the electromagnetic spectrum. A majority of the photons of the incident radiation are elastically scattered by the analyte. In other words, the scattered photons have the same energy, and thus the same wavelength, as the incident photons. However, a very small fraction of the photons are inelastically scattered by the analyte. Typically, only about 1 in 107 of the incident photons are inelastically scattered by the analyte. These inelastically scattered photons have a wavelength that differs from the wavelength of the incident photons. This inelastic scattering of photons is termed “Raman scattering”. The Raman scattered photons can have wavelengths less than, or, more typically, greater than the wavelength of the incident photons.
When an incident photon collides with the analyte, energy can be transferred from the photon to the molecules or atoms of the analyte, or from the molecules or atoms of the analyte to the photon. When energy is transferred from the incident photon to the analyte, the Raman scattered photon will have a lower energy and a corresponding longer wavelength than the incident photon. These Raman scattered photons having lower energy than the incident photons are collectively referred to in Raman spectroscopy as the “Stokes radiation.” A small fraction of the analyte molecules or atoms can be in an energetically excited state when photons are incident thereon. When energy is transferred from the analyte to the incident photon, the Raman scattered photon will have a higher energy and a corresponding shorter wavelength than the incident photon. These Raman scattered photons having higher energy than the incident photons are commonly referred to in Raman spectroscopy as the “anti-Stokes radiation.” The Stokes radiation and the anti-Stokes radiation collectively are referred to as the Raman scattered radiation or the Raman signal.
The Raman scattered radiation is detected by a detector that typically includes a wavelength-dispersive spectrometer and a photomultiplier for converting the energy of the impinging photons into an electrical signal. The characteristics of the electrical signal are at least partially a function of both the energy of the Raman scattered photons (as evidenced by their wavelength, frequency, or wave number) and the number of the Raman scattered photons (as evidenced by the intensity of the Raman scattered radiation). The electrical signal generated by the detector can be used to produce a spectral graph illustrating the intensity of the Raman scattered radiation as a function of the wavelength of the Raman scattered radiation. Analyte molecules and materials generate unique Raman spectral graphs. The unique Raman spectral graph obtained by performing Raman spectroscopy can be used for many purposes, including identification of an unknown analyte, or determination of physical and chemical characteristics of a known analyte.
Raman scattering of photons is a weak process. As a result, powerful, costly laser sources typically are used to generate high intensity incident radiation to increase the intensity of the weak Raman scattered radiation for detection. Surface-enhanced Raman spectroscopy (SERS) is a technique that allows for enhancement of the intensity of the Raman scattered radiation relative to conventional Raman spectroscopy. In SERS, the analyte molecules typically are adsorbed onto or placed adjacent to what is often referred to as a SERS-active structure. SERS-active structures typically include a metal surface or structure. Interactions between the analyte and the metal surface may cause an increase in the intensity of the Raman scattered radiation. The mechanism by which the intensity of the Raman scattered radiation is enhanced is not completely understood.
Several types of metallic structures have been employed in SERS techniques to enhance the intensity of Raman scattered radiation that is scattered by an analyte adjacent thereto. Some examples of such structures include electrodes in electrolytic cells, metal colloid solutions, and metal substrates such as a roughened metal surface or metal “islands” formed on a substrate. For example, it has been shown that adsorbing analyte molecules onto or near a specially roughened metal surface of gold or silver can enhance the Raman scattering intensity by factors of between 103 and 106.
Raman spectroscopy recently has been performed employing randomly oriented nanoparticles, such as nanometer scale needles, particles, and wires, as opposed to a simple roughened metallic surface. This process will be referred to herein as nano-enhanced Raman spectroscopy (NERS). Furthermore, structures comprising nanoparticles that are used to enhance the intensity of Raman scattered radiation may be referred to as NERS-active structures. The intensity of the Raman scattered photons from a molecule adsorbed on such a nanostructure can be increased by factors as high as 1016. At this level of sensitivity, NERS has been used to detect single molecules. Detecting single molecules with high sensitivity and molecular specificity is of great interest in the fields of chemistry, biology, medicine, pharmacology, and environmental science.
Hyper-Raman spectroscopy is another Raman spectroscopy technique that involves detecting higher order wavelengths of Raman scattered radiation. The hyper-Raman scattered radiation is Raman shifted relative to integer multiples of the wavelength of the incident electromagnetic radiation. Hyper-Raman scattered radiation can provide information about the analyte that cannot be obtained from simple Raman spectroscopy. The intensity of the hyper-Raman scattered radiation, however, is even less than the intensity of the Raman scattered radiation. As a result, hyper-Raman spectroscopy typically is performed using SERS-active or NERS-active structures.
Photonic Crystals
Photonic crystals are a new class of man-made materials. They are often referred to as “metamaterials.” Photonic crystals are formed by dispersing a material of one dielectric constant periodically within a matrix having a different dielectric constant. A one-dimensional photonic crystal is a three-dimensional structure that exhibits periodicity in dielectric constant in only one dimension. Bragg mirrors are an example of a one-dimensional photonic crystal. The alternating thin layers have different dielectric constants and refractive indices. The combination of several thin layers forms a three-dimensional structure that exhibits periodicity in dielectric constant in only the direction orthogonal to the planes of the thin layers. No periodicity is exhibited in either of the two dimensions contained within the plane of the layers.
A two-dimensional photonic crystal can be formed by periodically dispersing rods or columns of a material of one dielectric constant within a matrix having a different dielectric constant. Two-dimensional photonic crystals exhibit periodicity in only two dimensions, i.e., the directions perpendicular to the length of the rods or columns, but no periodicity is exhibited in the direction parallel to the length of the columns.
Finally, a three-dimensional photonic crystal can be formed by periodically dispersing small spheres or other spatially confined areas of a first material having a first dielectric constant within a matrix of a second material having a second, different, dielectric constant. Three-dimensional photonic crystals exhibit periodicity in dielectric constant in all three dimensions within the crystal.
Photonic crystals may exhibit a photonic bandgap over a range of frequencies in directions exhibiting periodicity in dielectric constant. In other words, there may be a range of frequencies of electromagnetic radiation that will not be transmitted through the photonic crystal in the directions exhibiting periodicity in dielectric constant. This range of frequencies that are not transmitted is known as a photonic bandgap of the photonic crystal. No photonic bandgap is exhibited in directions that do not exhibit periodicity in dielectric constant.
When defects are introduced into the periodic dielectric structure of a photonic crystal, localized electromagnetic modes may be allowed at frequencies within the photonic bandgap. For example, resonant cavities have been formed in photonic crystals by introducing point defects into the periodic dielectric structure, and waveguides have been formed in photonic crystals by introducing line defects into the periodic dielectric structure.